Electrochemical Series

1.Electrochemical Series
Electrochemical series also sometimes referred to as activity series is a list that describes the
arrangement of elements in order of their increasing electrode potential values. The series has
been established by measuring the potential of various electrodes versus standard hydrogen
electrode (SHE).

In electrochemical series, the electrodes (metals and non-metals) in contact with their ions are
arranged on the basis of the values of their standard reduction or oxidation potentials. Standard
electrode potential is obtained by measuring the voltage when the half cell is connected to the
standard hydrogen electrode under standard conditions.

2. Electropositive and Electronegative Elements

Elements (other than hydrogen) that display a greater tendency to lose electrons to their solution
are usually categorized as electropositive. Similarly, elements that acquire electrons are said to be
electronegative. They are usually below the element hydrogen in the series. In any case, if we
look at the electrochemical series, we can figure out the order in which metals will replace one
another from their salts. So, electropositive metals generally replace hydrogen from acids.

3. Electrochemical Series Important Points

Here are some of the important points to remember from this lesson.

 In the electrochemical series, the reduction potential of an element is taken in reference to

the hydrogen scale where Eo = zero. As per the definition, the standard reduction
potential of an element is described as the measure of the tendency of an element to
undergo reduction.
 The greater the reduction potential of an element the more easily it will be reduced.
Meanwhile, elements that have low reduction potential will get oxidized much quickly
and easily.
 Alternatively, elements who give up electrons without any difficulty have negative or
lower reduction potential. Elements that do not give up electrons easily rather they accept
electrons effortlessly have positive) or higher reduction potential.
 Stronger reducing agents that have negative standard reduction potential are usually
situated below the hydrogen in the electrochemical series. On the other hand, weaker
reducing agents with positive standard reduction potential are found above the hydrogen
in the series.
 As we move down in the group the reducing agent’s strength increases while the
oxidizing agents’ strength decreases.
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  Likewise, as we move from top to bottom in the series, the electro positivity and activity
of metals amplify or intensifies. In the case of nonmetals, it decreases.
4. Characteristics of Electrochemical Series
 The substances which are stronger reducing agents than hydrogen are placed above
hydrogen in the series and have negative values of standard reduction potentials.
 All those substances which have positive values of reduction potentials and placed below
hydrogen in the series are weaker reducing agents than hydrogen.
 The substances which are stronger oxidizing agents than H + ion are placed below
hydrogen in the series.
 The metals on the top (having high negative values of standard reduction potentials) have
the tendency to lose electrons readily. These are active metals.
 The activity of metals decreases from top to bottom.
 The non-metals on the bottom (having high positive values of standard reduction
potentials)
 Have the tendency to accept electrons readily. These are active non-metals.
 The activity of non-metals increases from top to bottom.
5. Electrochemical Series Chart
The Electrochemical series PDF chart is a simple way of visualizing similar vs. dissimilar
metals. For roofers, you need to know what compatibility issues exist in regards to material. In
this chart, common roofing metals (as well as uncommon) are shown. In most basic terms,
metals that exist further apart from each other on this scale will react with a higher propensity for
corrosion than ones that are close together. (i.e. Zinc and Copper = far apart on the scale. This
means you would never have a copper pipe draining water onto a zinc-coated roof).

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6. Application of Electrochemical Series
6.1 Reactivity of Metals
 The activity of the metal depends on its tendency to lose electron or electrons, i.e.,
tendency to form cation (M"+). This tendency depends on the magnitude of standard
reduction potential.
 The metal which has high negative value (or smaller positive value) of standard reduction
potential readily loses the electron or electrons and is converted into cation. Such a metal
is said to be chemically active.
 The chemical reactivity of metals decreases from top to bottom in the series. The metal
higher in the series is more active than the metal lower in the series. For example,
 Alkali metals and alkaline earth metals having high negative values of standard reduction
potentials are chemically active. These react with cold water and evolve hydrogen. These
readily dissolve in acids forming corresponding salts and combine with those substances
which accept electrons.
 Metals like Fe, Pb, Sn, Ni, Co, etc., which lie a little down in the series do not react with
cold water but react with steam to evolve hydrogen.
 Metals like Cu, Ag and Au which lie below hydrogen are less reactive and do not evolve
hydrogen from water.

6.2 Oxidizing Nature of Nonmetals

Oxidizing nature depends on the tendency to accept electron or electrons. More the value of
reduction potential, higher is the tendency to accept electron or electrons. Thus, oxidizing nature
increases from top to bottom in the electrochemical series. The strength of an oxidizing agent
increases as the value of reduction potential becomes more and more positive.

F2 (Fluorine) is a stronger oxidant than Cl2, Br2 and I2.

Cl2 (Chlorine) is a stronger oxidant than Br2 and I2.

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6.3 Reducing Power of Metals
Reducing nature depends on the tendency of losing electron or electrons. More the negative
reduction potential, more is the tendency to lose electron or electrons. Thus, reducing nature
decreases from top to bottom in the electrochemical series. The power of the reducing agent
increases as the standard reduction potential becomes more and more negative.

Sodium is a stronger reducing agent than zinc and zinc is a stronger reducing agent than iron.

6.4. Calculation of Standard emf (E0) of Electrochemical Cell

The standard emf of the cell is the sum of the standard reduction potential of the two half cell:
reduction half cell and oxidation half cell

Eocell = Eored + Eoox

By convention, the standard oxidation potential is always expressed in terms of reduction

potential.

Thus, standard oxidation potential (Eoox) = – standard reduction potential Eored

Therefore,

Eocell = (standard reduction potential of reduction half cell) – (standard reduction potential of

oxidation half cell)

As oxidation takes place at anode and reduction takes place at the cathode. Hence,  

Eocell = Eocathode – Eoanode

Example:

For a reaction, 2Ag+ (aq) + Cd → 2Ag + Cd+2(aq)

The standard reduction potential given is: Ag+/ Ag =0.80 volt, Cd+2/ Cd = -0.40 volt

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From the reaction, we can see that Cd losses electron and Ag+ gains. Hence, oxidation half cell or
anode is Cd.

Using the formula,

Eocell = Eocathode – Eoanode

             =0.80 - (-0.40)

             = 1.20 volt

6.5. Predicting the Feasibility of Redox Reaction

Any redox reaction would occur spontaneously if the free energy change (ΔG) is negative. The
free energy is related to cell emf in the following manner:

ΔGo = nFEo

Where n is the number of electrons involved, F is the Faraday constant and Eo is the cell emf. 

ΔGo can be negative if Eo is positive.

When Eo is positive, the cell reaction is spontaneous and serves as a source of electrical energy.

If it comes out to be negative then the spontaneous reaction cannot take place.

The resultant value of Eo for redox reaction is important in predicting the stability of a metal salt
solution when stored in another metal container.

For example, let us find out whether we can store copper sulphate solution in a nickel vessel or
not.

Given: Ni+2/ Ni = -0.25 volt, Cu+2/Cu = 0.34 volt

Ni + CuSO4 → NiSO4 + Cu

We want to see whether Ni metal will displace copper from copper sulphate solution to give
NiSO4 by undergoing oxidation reaction.

Ni(s) + Cu+2(aq) → Ni+2(aq) + Cu(s)

From the above reaction, it is clear oxidation terminal will be Ni electrode.

 Eocell = Eocathode – Eoanode

= 0.34 – (-0.25)

= 0.59 volt

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As the emf comes out to be positive, it implies copper sulphate reacts when placed in a
nickel vessel and hence cannot be stored in it.

6.6. Predicting the Product of Electrolysis

In case, two or more types of positive and negative ions are present in solution,
during electrolysis certain metal ions are discharged or liberated at the electrodes in preference to
others. In general, in such competition, the ion which is a stronger oxidizing agent (high value of
standard reduction potential) is discharged first at the cathode.

Thus, when an aqueous solution of NaCl containing Na +, Cl-, H+ and OH- ions is electrolyzed, 
H+ ion is preferentially deposited at cathode (reduction)  instead of Na+ being reduced, this is
because reduction potential of hydrogen( 0.00 volt) is higher than the reduction potential of
sodium( -2.71 volt). At the anode where oxidation takes place, the anion that has lower reduction
potential will be oxidized. Therefore, OH- with standard reduction potential 0.40 volt will be
oxidized in preference to Cl- with standard reduction potential of 1.36 volt.

6.7. Electropositive Character of Metals

The electropositive character also depends on the tendency to lose electron or electrons. Like
reactivity, the electropositive character of metals decreases from top to bottom in the
electrochemical series. On the basis of standard reduction potential values, metals are divided
into three groups:

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 Strongly electropositive metals: Metals having standard reduction potential near about -2.0
volt or more negative like alkali metals, alkaline earth metals are strongly electropositive in
nature.

Moderately electropositive metals: Metals having values of reduction potentials between

0.0 and about -2.0 volt are moderately electropositive. Al, Zn, Fe, Ni, Co, etc., belong to this
group.

Weakly electropositive metals: The metals which are below hydrogen and possess positive
values of reduction potentials are weakly electropositive metals. Cu, Hg, Ag, etc., belong to this
group.

7. Solved Problems
Predict whether the following reaction will occur spontaneously or not:

Fe+3 + 2Cl– → Fe+2 + Cl2

E0Fe+2/Fe = -0.440 volt ; E0Cl / Cl –= 1.36 volt

Solution:

Eocell = Eocathode – Eoanode

Since chlorine has higher reduction potential than iron therefore at cathode reduction of chlorine
occurs and oxidation of iron occurs at the anode.

Eocell = 1.36 -(-0.440) = 1.80 volts

The positive value of E0Cell implies that reaction occurs spontaneously.

The standard reduction potential at 250 ℃ for the following half-reaction are given below:

Zn+2(aq) + 2e– → Zn(s);       -0.76 volt

Cr+3 (aq) + 3e–→ Cr(s);        -0.740 volt

Cu+2(aq) + 2e– → Cu(s);       0.34 volt

Fe+3 + e– → Fe+2  ;                 0.77 volt

Which is the strongest reducing agent?

 Zn
 Cr
 Cu
 Fe+3

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Solution: Option 1

Reducing agent is a chemical species that loses an electron to another chemical species in a
redox chemical reaction. Since, reducing agent loses electron so it is oxidized. Out of the
following given half-reaction, the reduction of Zn+2 has the lowest reduction potential (-0.762).

We know that

Oxidation potential = - (reduction potential)

So in terms of standard oxidation potential Zinc will have the highest oxidation potential i.e,
0.762 volts. Therefore, zinc is the strongest reducing agent.

3. The standard oxidation potential, E0 for the half-reactions are as follows,

Cu → Cu+2 + 2e–   ;  E0 = -0.34 volts

Fe → Fe+2 + 2e–   ; E0 = 0.41 volts

Calculate the emf of the cell, Cu+2 + Fe → Cu + Fe+2

Solution: 

Eocell = (standard reduction potential of reduction half cell) – (standard reduction  potential of
oxidation half cell)

Eocell = -(standard oxidation  potential of reduction half cell) – (-standard oxidation  potential of
oxidation half cell)

Eocell = -0.34-(-0.41)

Eocell = 0.07 volt.